WO2019019533A1 - Produit de nettoyage et son procédé de préparation et d'utilisation - Google Patents

Produit de nettoyage et son procédé de préparation et d'utilisation Download PDF

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Publication number
WO2019019533A1
WO2019019533A1 PCT/CN2017/116442 CN2017116442W WO2019019533A1 WO 2019019533 A1 WO2019019533 A1 WO 2019019533A1 CN 2017116442 W CN2017116442 W CN 2017116442W WO 2019019533 A1 WO2019019533 A1 WO 2019019533A1
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WIPO (PCT)
Prior art keywords
cleaning agent
corrosion inhibitor
mass fraction
cleaning
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/116442
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English (en)
Chinese (zh)
Inventor
王溯
蒋闯
冯强强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Xinyang Semiconductor Material Co Ltd
Original Assignee
Shanghai Xinyang Semiconductor Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Xinyang Semiconductor Material Co Ltd filed Critical Shanghai Xinyang Semiconductor Material Co Ltd
Priority to US16/488,001 priority Critical patent/US11549086B2/en
Publication of WO2019019533A1 publication Critical patent/WO2019019533A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/428—Stripping or agents therefor using ultrasonic means only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • H10P70/23—Cleaning during device manufacture during, before or after processing of insulating materials
    • H10P70/234—Cleaning during device manufacture during, before or after processing of insulating materials the processing being the formation of vias or contact holes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • H10P70/27—Cleaning during device manufacture during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers
    • H10P70/273—Cleaning during device manufacture during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers the processing being a delineation of conductive layers, e.g. by RIE
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/41—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their conductive parts
    • H10W20/44—Conductive materials thereof
    • H10W20/4403—Conductive materials thereof based on metals, e.g. alloys, metal silicides
    • H10W20/4405—Conductive materials thereof based on metals, e.g. alloys, metal silicides the principal metal being aluminium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/41—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their conductive parts
    • H10W20/44—Conductive materials thereof
    • H10W20/4403—Conductive materials thereof based on metals, e.g. alloys, metal silicides
    • H10W20/4421—Conductive materials thereof based on metals, e.g. alloys, metal silicides the principal metal being copper

Definitions

  • the invention relates to a cleaning agent, a preparation method and application thereof.
  • photolithography is used to image the pattern onto the device wafer.
  • Photolithographic techniques include coating, exposure, and development steps.
  • the wafer is coated with a positive or negative photoresist material and then covered with a mask that defines the pattern to be held or removed in a subsequent process.
  • a bundle of monochromatic radiation such as ultraviolet (UV) light or deep UV (DUV) light ( ⁇ 250 nm or 193 nm)
  • UV light ultraviolet
  • DUV deep UV
  • the ground is soluble in the selected rinse solution.
  • the soluble photoresist material is then removed or "developed" leaving the same pattern as the mask.
  • vapor phase plasma etching is used to transfer the pattern of the developed photoresist coating to the underlying layer, which may include a hard mask, an interlayer dielectric, and/or an etch stop layer.
  • Residues after plasma etching are typically deposited on the structure of the back end wiring, which may interfere with subsequent silicidation or contact formation if not removed.
  • the residue after plasma etching ashing usually includes various residues such as hard mask residues, polymer residues, and other particles.
  • the cleaning agent is required to have high selectivity, for example, the hard mask can be removed efficiently with little influence on the metal and the low-k dielectric material.
  • the nitride of the residue are needed as device critical dimensions continue to shrink and corresponding requirements for high production efficiency and reliable equipment performance.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior cleaning agent for removing the ruthenium-containing etch mask material (such as tantalum nitride), and to provide a cleaning agent, a preparation method thereof and an application thereof.
  • the cleaning agent of the invention can remove the nitride of the hard mask residue efficiently with little influence on the metal and the low-k dielectric material, has good selectivity, and has a very broad market application prospect.
  • the present invention provides a cleaning agent which is prepared from a raw material comprising the following mass fraction components: 0.5% to 20% of an iodine-containing oxidizing agent, 0.5% to 20% of a boron-containing etchant, 1% to 50% of a pyrrolidone solvent, 1% to 20% of a corrosion inhibitor, 0.01% to 5% of a metal ion-free surfactant, and water, and the sum of the mass fractions of the components is 100%;
  • the pH of the cleaning agent is 7.5-13.5;
  • the corrosion inhibitor is a benzotriazole corrosion inhibitor, a bismuth corrosion inhibitor, a carbachol corrosion inhibitor, and a thiocarbazone corrosion inhibitor.
  • the corrosion inhibitor is a benzotriazole corrosion inhibitor, a bismuth corrosion inhibitor, a carbachol corrosion inhibitor, and a thiocarbazone corrosion inhibitor.
  • the mass fraction of the iodine-containing oxidizing agent is preferably from 1% to 10%, more preferably from 1.5% to 5%.
  • the mass fraction of the boron-containing etchant is preferably from 1% to 10%, more preferably from 1.5% to 5%.
  • the mass fraction of the pyrrolidone solvent is preferably from 5% to 35%, more preferably from 10% to 30%.
  • the mass fraction of the corrosion inhibitor is preferably from 3% to 15%, more preferably from 5% to 10%.
  • the mass fraction of the surfactant is preferably from 0.1% to 4%, more preferably from 0.2% to 3%.
  • the pH of the cleaning agent is preferably from 8 to 12, more preferably from 9 to 11.
  • the sum of the mass fractions of the components is 100%, so the amount of water is preferably 100% of the sum of the mass fractions of the components.
  • the iodine-containing oxidizing agent is preferably one or more of iodic acid, iodate, periodic acid and periodate.
  • the iodate salt is preferably ammonium iodate and/or tetramethylammonium iodate.
  • the periodate is preferably ammonium periodate and/or tetramethylammonium periodate.
  • the boron-containing etchant can be a boron-containing etchant conventional in the art, preferably tetrafluoroboric acid, ammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropyltetrafluoroborate One or more of ammonium and tetrabutylammonium tetrafluoroborate.
  • the pyrrolidone solvent is a pyrrolidone solvent which is conventional in the art, and is preferably a hydrogen-substituted pyrrolidone solvent on N.
  • the hydrogen-substituted pyrrolidone solvent on the N is preferably one or more of N-methylpyrrolidone, N-ethylpyrrolidone, N-cyclohexylpyrrolidone, and N-hydroxyethylpyrrolidone.
  • the benzotriazole corrosion inhibitor is preferably one or more of benzotriazole, methylbenzotriazole and 5-carboxybenzotriazole.
  • the guanidine-based corrosion inhibitor is preferably acetophenone benzoquinone.
  • the thiocarbazone-based corrosion inhibitor is preferably diphenylthiocarbazone.
  • the metal ion-free surfactant is a conventional metal ion-free surfactant in the art, preferably polyvinylpyrrolidone and/or dodecylbenzenesulfonic acid.
  • the pH can be adjusted according to the actual conditions of each component and content in the cleaning agent.
  • one or more of an organic acid, an inorganic acid, an inorganic base, a strong base weak acid salt, and a buffer solution can be used. If the pH of the degumming agent is prevented from fluctuating drastically, it can be adjusted using a buffer solution conventional in the art.
  • the organic acid is preferably citric acid.
  • the inorganic acid is preferably boric acid.
  • the strong base weak acid salt is preferably tetramethylammonium hydroxide.
  • the water is preferably one or more (for example, two kinds) of deionized water, distilled water, pure water, and ultrapure water.
  • the cleaning agent is prepared from a raw material consisting of 0.5% to 20% of an iodine-containing oxidizing agent and 0.5% to 20% of a boron-containing etchant. , 1%-50% pyrrolidone solvent, 1%-20% corrosion inhibitor, 0.01%-5% metal ion-free surfactant and water, the sum of the mass fractions of each component is 100%;
  • the cleaning agent has a pH of 7.5-13.5;
  • the corrosion inhibitor is a benzotriazole corrosion inhibitor, a bismuth corrosion inhibitor, a carbachol corrosion inhibitor, and a thiocarbazone corrosion inhibitor. One or more of them.
  • the cleaning agent is prepared from a raw material consisting of 1% to 10% of an iodine-containing oxidizing agent and 1% to 10% of a boron-containing etchant. 5%-35% pyrrolidone solvent, 3%-15% corrosion inhibitor, 0.1%-4% metal ion-free surfactant and water, the sum of the mass fractions of each component is 100%;
  • the cleaning agent has a pH of 8-12;
  • the corrosion inhibitor is a benzotriazole corrosion inhibitor, a bismuth corrosion inhibitor, a carbachol corrosion inhibitor, and a thiocarbazone corrosion inhibitor. One or more of them.
  • the cleaning agent is prepared from a raw material comprising 1.5% to 5% of an iodine-containing oxidizing agent and 1.5% to 5% of a boron-containing etchant.
  • the pH of the cleaning agent is 9-11;
  • the corrosion The inhibitor is one or more of a benzotriazole corrosion inhibitor, a quinone corrosion inhibitor, a carbachol corrosion inhibitor, and a thiocarbazone corrosion inhibitor.
  • the present invention also provides a method for preparing the cleaning agent, which comprises the steps of: mixing the raw materials.
  • the mixing is preferably carried out by adding the solid component of the raw material component to the liquid component and stirring uniformly.
  • the temperature of the mixing is room temperature. After the mixing, it is preferred to further include an operation of shaking and filtering.
  • the purpose of the oscillation is to sufficiently mix the raw material components, and the oscillation speed and time are not limited. Filtration is to remove insolubles.
  • the invention also provides an application of the cleaning agent in cleaning and etching ashed semiconductor chips.
  • the semiconductor chip is preferably a semiconductor chip of a copper interconnect or an aluminum interconnect structure.
  • the application preferably includes the steps of contacting the etched ashed semiconductor chip with the etch cleaning agent. More preferably, the method comprises the steps of: contacting the etched and ashed semiconductor chip with the etch cleaning agent, shaking, washing, and drying.
  • the temperature of the contact is preferably from 10 ° C to 90 ° C, preferably from 20 ° C to 60 ° C, for example from 40 to 45 ° C.
  • the operation of the contact preferably immerses the etched and ashed semiconductor chip in the cleaning liquid.
  • the oscillations preferably oscillate in a constant temperature oscillator.
  • the temperature of the oscillation is preferably from 10 ° C to 90 ° C, preferably from 20 ° C to 60 ° C, for example from 40 to 45 ° C.
  • the washing is preferably washed with water (for example one or more of deionized water, distilled water, pure water and ultrapure water).
  • the drying method is preferably blown dry with high purity nitrogen.
  • room temperature means 10-30 °C.
  • the reagents and starting materials used in the present invention are commercially available.
  • the positive progress of the present invention is that the cleaning agent prepared by the preparation method of the invention can remove the nitride efficiently with less influence on the metal and the low-k dielectric material, has good selectivity and good cleaning effect. It has a very broad market application prospect, solves the problem for microelectronics enterprises, plays a positive role in promoting the development of China's microelectronics industry, and also has high economic benefits.
  • the preparation method of the cleaning agent comprises the steps of: mixing the corresponding raw materials.
  • the specific operating temperatures are not limited, and all are carried out under room temperature conditions.
  • Comparative Example 1-2 the effect of not adding the iodine-containing oxidizing agent was explored in Comparative Examples 3-8; the effect of not adding the boron-containing etchant was explored in Comparative Examples 9-14; Comparative Examples 15-21 explored the effect of using an oxidizing agent other than the iodine-containing oxidizing agent; Comparative Examples 22-27 explored the effects of using an etchant other than the boron-containing etchant; Comparative Examples 28-29 explored the use of pyrrolidone Effect of other types of organic solvents other than solvents; Comparative Examples 30-31 explored the effects of using other corrosion inhibitors other than corrosion inhibitors in the compositions of the present invention; Comparative Examples 32-33 explored the use of surfaces containing metal ions The effect of the active agent.
  • the cleaning agent of the present invention has an improvement over the cleaning agent of the comparative example, both in terms of etching selectivity and cleaning effect.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

L'invention concerne un produit de nettoyage, et son procédé de préparation et d'utilisation. Le produit de nettoyage est préparé à partir des produits bruts suivants comprenant la fraction massique suivante de composants : 0,5 % à 20 % d'un oxydant contenant de l'iode, 0,5 % à 20 % d'un agent de gravure contenant du bore, 1 % à 50 % d'un solvant de pyrrolidinone, 1 % à 20 % d'un inhibiteur de corrosion, 0,01 % à 5 % d'un tensioactif exempt d'ions métalliques, et de l'eau, la somme de la fraction massique de chaque composant étant de 100 %; le pH du produit de nettoyage est compris entre 7,5 et 13,5; et l'inhibiteur de corrosion est un ou plusieurs des inhibiteurs suivants: benzotriazole, hydrazone, carbazone et thiocarbohydrazone. Le produit de nettoyage peut éliminer efficacement des nitrures de résidus de masque dur avec peu d'effets sur les métaux et les matériaux diélectriques à faible constante (low-κ), et présente une bonne sélectivité.
PCT/CN2017/116442 2017-07-25 2017-12-15 Produit de nettoyage et son procédé de préparation et d'utilisation Ceased WO2019019533A1 (fr)

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CN201710613216.9A CN107357143B (zh) 2017-07-25 2017-07-25 一种清洗剂、其制备方法和应用

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CN107357143A (zh) 2017-11-17
CN107357143B (zh) 2018-06-19

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